Chalmers originally hails from Utica, New York,[5] but has also said that he comes from Queens, New York and Intercourse, Pennsylvania. He attended Ball State University and is a proud owner of a red 1979 Honda Accord (and later, a Camry, which Otto Mann promptly wrecks). He mentioned to Principal Skinner that he is a Sagittarius (b. November 22-December 22).[6]

Chalmers used to teach, until he supervised a group of detention students called The Fight Club and they beat him up when he mistakenly called them "The Breakfast Club". After this, he never taught again and only superintended. Years later, he ended up teaching Bart Simpson and several other students about Theodore Roosevelt when Principal Skinner challenged him to take over Bart's education.[3]

Chalmers is a strict, no-nonsense, and largely humorless man, with a short temper and low tolerance for disorder or rule-breaking. His general demeanor and personality are like those of a military officer. Whenever he visits Springfield Elementary, some sort of disaster strikes. He produces extreme anxiety in Principal Skinner, who offers increasingly improbable stories to explain what is happening. Chalmers is known for throwing open the doors to the room and bellowing "SKINNER!!!" or "SEYMOUR!!!", to which Seymour's usual response is to stammer "S-Superintendent Chalmers!" Evidently, Chalmers' trademark bellowed catchphrase has caused some paranoia in Skinner.[7]

Chalmers's own competence and dedication to his job are questionable. He let Ned Flanders allow the school to descend into anarchy when he was principal, freely admitting that he had fired Skinner for far less, explaining simply that "Skinner really bugged me." In fact, the only reason Chalmers even allowed Skinner to be reinstated as Principal was because Ned Flanders introduced prayer into the school, and thus was fired because Chalmers felt that religion should never be placed within school walls, just as school or government shouldn't be placed in church walls. He seems disturbingly unconcerned with the school's decline, saying that "the way America's public schools are sliding, they'll all be like this in a matter of months. I say enjoy it — it's a hell of a toboggan ride!" He also promotes people based on personal bias as opposed to actual competence, promoting Principal Holloway, described by Skinner as a "drunk" and Chalmers as a "pill-popper", to assistant superintendent, overlooking the efforts made by Skinner to improve his school's standing.

Chalmers with a bald head

When Springfield began erecting surveillance cameras around Springfield and 742 Evergreen Terrace was discovered to be a blind spot and transformed into a crowding place for rebellious activity, Superintendent Chalmers was spotted swinging nunchucks while prancing in a Tutu.[8]

He was once involved in a large brawl in the teacher's lounge and was knocked out after Dewey Largo punched him over a wooden balcony.

Chalmers and Skinner have also made Chalmskinn Productions, an organization that the two school workers make when they sponsor Lisa in a film competition.

Chalmers once dated Agnes Skinner, much to Skinner's dismay[9] (although on other occasions he has mentioned being married). Later, it is revealed that Chalmers is a widower and his wife's name was Rosemary.[3]

On a few occasions, Chalmers says Skinner's name this way when absolutely nothing has gone wrong, implying that he probably pronounces Skinner's name this way out of habit (e.g. once saying "SKINNNEERR! and Mrs. SKINNNEERR!") This habit seems to also have an effect on words that rhyme with "Skinner", such as "I must get home to make sure my pool boy is using his SKIMMMEERR!", "...catch a fish for his DINNNEERR!" and "SPINNNEERR" after yelling at Bart Simpson for spinning in Skinner's chair.

In one possible future, Chalmers is practically a vegetable, wheelchair-bound and only capable of saying his trademark line: "Skinner!"[13]

In another possible future, Chalmers is a colonel of an army that he leads on the planet Rigel 7 to fight the Rigellians, to get Hillarium, a liquid that makes everything funny. He is defeated after Bart makes Chalmers slap himself in a large robot suit that he controls by movement, telling him he had something on his face, thus making Chalmers fall off a cliff.[14]

In the DVD commentary for "22 Short Films About Springfield", Simpsons creators noted that Superintendent Chalmers seems to be one of the few "normal" characters on the show, and Chalmers is frequently alone in his awareness of the show's zaniness.